Process for washing and bleaching compositions therefor



FIP83 SR unuoo nttttttittit Stt'itf'fiit 09 xs 2,898,181 51 UnitedStates Patent PROCESS FOR WASHING AND BLEACHING COMPOSITIONS THEREFORKarl Dithmar, Frankfurt am Main, and Ulrich Holfmann, Bad Homhurg(Taunus), Germany, assignors to Deutsche Goldund Silber-Scheideanstaltvormals Roessler, Frankfurt am Main, Germany No Drawing. ApplicationOctober 23, 1957 Serial No. 691,802

Claims priority, application Germany May 20, 1953 4 Claims. (Cl. 8-137)The present invention relates to a novel washing process andcompositions therefor, and more particularly to a washing processemploying washing compositions containing perborate bleaching agents,preferably sodium perborate, and washing compositions particularlyadapted therefor.

Textile fibers and textiles produced therefrom, especially when naturalvegetable fibers such as cotton or linen are concerned, are often washedby a procedure in which the goods to be washed are introduced into awashing bath at room or slightly raised temperatures containing thenormal surface active washing agents, such as soaps or syntheticdetergents which also can contain inorganic builders and fillers, suchas alkalies, water glass, phosphates, sulfates, peroxide compounds andthe like, and slowly raising the temperature of the bath to about theboiling point and maintaining the bath at such temperature for sometime. This customary boiling method is not only troublesome andexpensive, but also, when goods are washed which are partly orcompletely produced from delicate fibers, such as artificial silk,regenerated cellulose staple fibers or fully synthetic fibers, there isa danger of fiber damage. Consequently, attempts have been made toprovide washing procedures which could be carried out at lowertemperatures than boiling temperatures, but they have not met with verysatisfactory results. It was found that the optimum cleaning effect ofthe usual washing agents on cellulosic fibers is only attained at ornear the boiling point of the washing fluid, so that when lowertemperatures are employed insufficient cleaning efiects are obtained.When so-called self-actin or automatic washing compositions whichnormally contain perborates, such as sodium perborate, are employed attemperatures below those at or near the boiling point, for example, at60-70 C., an insufficient bleaching effect is obtained, for thestability of commercial perborates is normally so adjusted that theyonly give oif their active oxygen to the fiber at high temperatures.

In accordance with the invention, it was unexpectedly discovered thatthe addition of certain carboxylic acid amides to washing compositionscontaining washing agents (organic surface active compounds which reducethe surface tension of water) and perborate bleaching agents improvedsuch washing compositions so that they have a good cleaning action aswell as a good bleaching action at temperatures lower than boilingtemperatures, for example, at about 60-70 C. With such Washingcompositions, the cleaning and bleaching effects obtained attemperatures of about 6070 C. were about the same as attainable withwashing compositions not containing an amide activator at temperaturesof about 95100 C. The amide activators employed according to theinvention, it was found, have the property of increasing the oxygenliberated by the perborates. It was, for example, determined that awashing bath containing a perborate containing washing composition towhich 0.5 g./l. of formamide had been added only contained 25% of itsoriginal 2,898,181 Patented Aug. 4, 1959 active oxygen content after twohours at 60 0., whereas in the absence of formamide such bath, otherwiseunder the same conditions, still contained of the original active oxygencontent. Consequently, in the bath containing formarnide the quantity ofoxygen given olf to the fibers is about three times that in a bath notcontaining the formamide.

The amides which have according to the invention been found particularlysuitable as activators in peroxide containing washing agents are thoseof saturated or unsaturated carboxylic acids containing 1 to 4 carbonatoms, for example, amides of formic, acetic, proprionic, butyric,acrylic and methacrylic acids. Such amides can be produced in the usualway by reacting the fatty acids or functional derivatives thereof withammonia or amines. The amides employed according to the invention mustbe soluble in water or washing solutions even if only to a slightextent. For this reason, it can be desirable to employ amides whoseamido group carries solubilizing substitutents, for example, thosederived from monoor diethanol amines.

The general formula of the amides suitable according to the invention isas follows:

in which R is selected from the group consisting of hydrogen andaliphatic hydro-carbon radicals containing 1 to 3 carbon atoms and R andR" are selected from the group consisting of hydrogen and C H OH.

The acrylamides and methacrylamides are especially suitable for thepurposes of the invention as they are stable, non-hydroscopic productswhich render it possible to produce stable storable washing powders. Thequantity of amide activator employed according to the invention can bebetween about 0.1 to 1.0 g. per liter of washing bath or in amounts ofabout 5 to 50%, preferably 10 to 25 of the organic surface activewashing agents, that is, of the soaps or synthetic detergents in thewashing bath or washing composition. 1

The organic surface active agents (washing agents), which form anessential part of the washing compositions and washing liquids accordingto the invention, as indicated can either be the commonly employedsoaps, such as the alkali metal soaps of fatty acids, such as stearicand palmitic acids, or of rosin acids, such as abietic acid, or theso-called synthetic detergents which the art usually considers apartfrom the ordinary soaps. With regard to what the art considers assynthetic detergents, reference is made to the article concerningsynthetic detergents by Donald Price, Chemical Week, October 22, 1955,pages 40-45, as well as the succeeding table of synthetic detergentsavailable on the market (pages 46-82).

The organic surface active agents employed as washing agents contain acombination of a hydrophilic moiety and a hydrophobic moiety and areclassified as being anionic, cationic or non-ionic. Both the anionic andcationic surface active agents are ionizable but differ in that in theanionic surface active agent the hydrophobic moiety is in the anion andthat in the catonic surface active agent the hydrophobic moiety is inthe cation. Ordinary soaps, such as sodium stearate and the like, aswell as synthetic detergents of the sulfonated or sulfated types, arewell known anionic surface active agents. Quaternary ammonium salts,such as cetyl pyridium chloride and the like, as well as salts oftertiary amines, such as, for example, compounds of the formula RCONHCHN C H .HC1

wherein RC0 is the acyl radical of a higher fatty acid, such as oleicacid, are typical cationic surface active agents. Polyoxyethylene estersof fatty acids, polyoxyethylene ethers of alkyl phenols,polyoxyethylene, fatty acid alkanol amine condensation products and thelike are typical non-ionic surface active agents.

In general, the most important organic surface active agents belong toone of the following types of compounds:

Soaps Aminocarboxylic acids Acylation products of aminocarboxylic acidsSalts of acid sulfuric acid esters Sulfated fatty acids and fatty acidderivatives Alkyl sulfates Salts of organic sulfonic acids Fatty acidsulfonates Alkyl sulfonic acids and their salts Alkyl aryl sulfonatesAliphatic-aromatic sulfonic acids Polyglycol ethers Polyglycol estersPolyalcohols Polyamines Alkylolamines The quantity of organic surfaceactive agent (washing agent) contained in the perborate and carboxylicacid amide washing compositions and washing baths according to theinvention can vary within wide limits. Experience has shown that onlyvery small quantities of such organic surface active agents are requiredto effect the activation action of the carboxylic acid amides upon theperborate. Nevertheless, in general, the quantity of the organic surfaceactive agent for practical purposes should be sufficient for efiicientsoil removal when such washing compositions or washing baths areemployed for washing. Consequently, the organic surface active agentcontent of the known generally employed perborate containing washingcompositions more than suflices to provide the activation action on thecarboxylic acid amides employed according to the invention. In the drywashing compositions, the organic surface active agent content can, forexample, be between about and about 80% and in the washing baths it can,for example, be between about 0.1 and 1%.

The quantity of perborate in the compositions according to the inventionpreferably is such that 0.2 to 5 grams of active oxygen are provided perliter of washing bath.

The following examples will serve to illustrate several modifications ofthe process and products of the invention:

Example 1 A washing solution was prepared by dissolving grams per literof a perborate containing washing powder of the following composition inwater:

% sodium perborate 5% powder sodium water glass 40% soap 20% sodiumsulfate 5% sodium carbonate 5% sodium pyrophosphate Three portions ofthis washing solution were taken, of which two contained no furtheraddition, whereas 0.5 g./l. of formamide was added to the third. One ofthe first two solutions and the third solution were heated at 60 C. andthe other of the first two solutions was heated at 95 C. for a number ofhours. Samples were taken from time to time from each of the threesolutions and titrated with a N/10 potassium permanganate solution toascertain the decline in the peroxide content of such solutions.

The following table gives the results of such tests:

I II III no addition no addition 0.5 g./l. Time, Minutes at C. at 60 O.formamide g./l. act. 0 g./l. act. 0 addition 60 0.- g [1. act. 0

Example 2 Cotton goods which had been given a standard soiling with sootand oil were introduced into an aqueous washing liquid containing 15g./l. of the washing powder disclosed in Example 1 and 0.5 g./l. offormamide at room temperature and the washing liquid heated in /z hourto 60 C. and heated at this temperature for /2 hour and then rinsed anddried. The ratio of cotton goods to bath was 1:30. A good washing andbleaching effect was achieved by such treatment. On the other hand, in acontrol test carried out under the same conditions, but with theomission of the formamide, it was found that a very noticably poorerwashing and bleaching effect was obtained.

In a further comparative test, in which the soiled cotton goods wereintroduced into a washing liquid containing no formamide at roomtemperature and the temperature of the washing liquid raised to 95 C. in/2 hour and maintained at this temperature for /2 hour, it was foundthat the same washing and bleaching effects were obtained as wereobtained with the 60 C. treatment with the formamide containing bathaccording to the invention.

Example 3 2.5% of acrylic acid amide was incorporated in a washingpowder of the composition given in Example 1, and a washing bath wasprepared containing 10 g./l. of such composition so that the bathcontained 0.25 g./l. of acrylic acid amide.

When such a washing bath was used to wash soiled cottion goods at atemperature of 60 C., the same washing and bleaching effect was obtainedas only could be in the absence of the acrylic acid amide addition at9() C. The oxygen liberated in the acrylic acid amide containing washingliquid at 60 C. also corresponded to that which was attainable in theabsence of the acrylic acid amide at 90100 C.

Similar results were obtained with washing baths in which the acrylicacid amide had been replaced by methacrylic acid amide. Perboratewashing compositions containing about 2.5 to 5% of acrylic acid ormethacrylic acid amide have been found admirably suited for washingpurposes. Good results were also obtained when 2.5 to 5% of acrylic acidamido ethanol or methacrylic acid amido ethanol were employed in placeof the acrylic or methacrylic acid amide. In each instance the incorporation of the amido compound rendered it possible to obtain good cleaningand bleaching effects at lower temperatures than were possible in theabsence of such amido compounds.

Example 4 A washing powder of the following composition was prepared:

of lauryl al- Example 5 Washing baths were prepared by dissolving thefollowing compositions in water at 60 C. The quantities of thecomponents are given in grams per liter of finished washing bath.

Composition 1a:

7.5 grams Marseilles soap 1.5 grams formamide 2.0 grams sodium perborateComposition lb:

7.5 grams Marseilles soap 2.0 grams sodium perborate Composition 2a:

4.0 grams sodium lauryl sulfate 2.0 grams formamide 3.0 grams sodiumperborate Composition 2b:

4.0 grams sodium lauryl sulfate 3.0 grams sodium perborate The activeoxygen content was measured right after the washing baths were preparedand the percentage of active oxygen retained in such baths after varyingperiods of time was measured, giving the following result:

Time, Minutes Oompo- Oompo- Compo- Composition 1a sition 1b sitlon 2asition 2b This is a continuation-impart of application Serial No.429,969, filed May 14, 1954, and now abandoned.

We claim:

1. In a process of washing textile materials with aqueous washingliquids containing an organic surface active washing agent and aperborate bleaching agent, the step which comprises incorporating analiphatic carboxylic acid amide of the formula R.CO.NR'R" in which R isselected from the group consisting of hydrogen and aliphatic hydrocarbonradicals containing 1 to 3 carbon atoms and R and R" are selected fromthe group consisting of hydrogen and C H OH in the washing liquidemployed to wash the textile, the quantity of such amide incorporatedbeing between 0.1 and 1 gram per liter of washing liquid, the quantityof perborate in said washing liquid providing 0.2 to 5 grams of activeoxygen per liter of washing liquid and the quantity of the organicsurface active agent in said washing liquid being between about 1 and 10grams per liter.

2. The process of washing textile materials according to claim 1 inwhich said washing liquid is maintained at a temperature between aboutand C.

3. In combination with an organic surface active agent and perboratebleaching agent containing washing composition for textiles, analiphatic carboxylic acid amide of the formula R.CO.NR'R in which R isselected from the group consisting of hydrogen and aliphatic hydrocarbonradicals containing 1 to 3 carbon atoms and R and R" are selected fromthe group consisting of hydrogen and -C H OH, the quantity of said amidebeing 0.1 to 1 part by weight per 1 to 10 parts by Weight of organicsurface active agent and the quantity of perborate providing 0.2 to 5parts by weight of active oxygen per 0.1 to 1 part by weight of theamide.

4. In combination with an organic surface active washing agent andperborate containing aqueous bath, an aliphatic carboxylic acid amide ofthe formula in which R is selected from the group consisting of hydrogenand aliphatic hydro-carbon radicals containing 1 to 3 carbon atoms and Rand R" are selected from the group consisting of hydrogen and -C H OH ina quantity of 0.1 to 1 g. per liter of such bath, the quantity oforganic surface active agent in said bath being 1 to 10 grams per literand the quantity of perborate providing 0.2 to 5 grams of active oxygenper liter of said bath.

References Cited in the file of this patent UNITED STATES PATENTS1,006,798 Schmidt Oct. 24, 1911 1,101,449 Kemmerich June 23, 19142,120,430 Reiche June 14, 1938 2,254,434 Lind et al. Sept. 2, 19412,730,428 Lindner Jan. 10, 1956 OTHER REFERENCES Folgner: Monatsehriftfiir Textile Industrie, October 1937, p. 257.

1. IN A PROCESS OF WASHING TEXTILE MATERIALS WITH AQUEOUS WASHINGLIQUIDS CONTAINING AN ORGANIC SURFACE ACTIVE WASHING AGENT AND APERBORATE BLEACHING AGENT, THE STEP WHICH COMPRISES INCORPORATING ANALIPHATIC CARBOXYLIC ACID AMIDE OF THE FORMULA R.CO.NR''R" IN WHICH R ISSELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALIPHATIC HYDROCARBONRADICALS CONTAINING 1 TO 3 CARBON ATOMS AND R'' AND R" ARE SELECTED FROMTHE GROUP CONSISTING OF HYDROGEN AND -C2H4OH IN THE WASHING LIQUIDEMPLOYED TO WASH THE TEXTILE, STHE QUANTITY OF SUCH AMIDE INCORPORATEDBEING BETWEEN 0.1 AND 1 GRAM PER LITER OF WASHING LIQUID, THE QUANTITYOF PERBORATE IN SAID WASHING LIQUID PROVIDING 0.2 TO 5 GRAMS OF ACTIVEOXYGEN PER LITER OF WASHING LIQUID AND THE QUANTITY OF THE ORGANICSURFACE ACTIVE AGENT IN SAID WASHING LIQUID BEING BETWEEN ABOUT 1 AND 10GRAMS PER LITER.